CN103298735B - Steam-hydrocarbon reforming with limited steam export - Google Patents
Steam-hydrocarbon reforming with limited steam export Download PDFInfo
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0816—Heating by flames
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
Abstract
A steam-hydrocarbon reforming process and apparatus wherein reformate from a prereformer is reacted in a gas heated reformer which is heated by reformed gas from primary reformer. Reformate from the gas heated reformer is passed to the primary reformer as feed gas.
Description
Background
The disclosure relates to steam-hydrocarbon reforming.Hydrogen and/or synthesis gas are produced by steam-hydrocarbon reforming.Steam-hydrocarbon reforming process produces steam usually as the means reclaiming heat and raising process efficiency.More specifically, the disclosure relates to compared with conventional plants, has steam-hydrocarbon reforming that steam that is limited or that reduce produces.
Synthesis gas for the production of product, such as ammonia, methyl alcohol and hydrogen.Produce synthesis gas by pyroprocess, wherein can utilize much used heat.Used heat is generally used for producing steam and contributes to improving the overall efficiency of synthesis gas equipment.In typical equipment, by useless thermogenetic steam amount significantly beyond in steam-hydrocarbon reformer for the amount of the steam needed for reforming hydrocarbon charging.Excess steam is exported or can be used to produce power in steam turbine.
But exporting steam needs expensive pipeline system, comprises control and safety valve, steam trap, heat tracking etc.When neighbouring need steam time and/or be willing to that meaning steam pays reasonable price as human consumer time, it is reasonable for exporting steam.Export steam and also can apply restriction to facility locations, minimize to make the length of steam output pipe line.
Equipment for the production of synthesis gas produces a large amount of steam by used heat.Depend on design, the many 35%-200% needed for the inside in the comparable steam-hydrocarbon reformer of overall steam production uses.Current industrial practice exports excessive steam or in steam turbine, uses steam for power generation.Two kinds of options all need other capital cost, and for do not have human consumer be ready with rational cost buy steam or can not be competitive produce the project of power, described option high cost.
Export irrational little hydrogen productive unit for steam, the excessive steam of a part is usually not too effectively for process or discharged.Hydrogen facility can design has less thermal recovery unit, causes not too effective facility.
There is many design options for changing total steam production and the output of reduction steam according to synthesis gas facility.These design options consider process restriction, the postcombustion requirement of such as catalytic steam reforming device.
Widely used option is that the combustion air being used for reformer is preheated to a high temperature, such as up to 600 DEG C (1100 °F).Combustion air is preheating in the convection section of reformer usually, and can be arranged as one or two stage of use, and this depends on the preheating temperature of expectation.Pre-heated combustion air contributes to reducing the amount of the required fuel of burning in reformer.Owing to using less fuel, the flue gas stream carrying out reformer unit reduces, and causes less used heat.
Preheating of fuel has similar but less impact for overall steam production.
Another option of * uses adiabatic pre-reformer.Adiabatic pre-reformer is the vessel being filled with Ni-based reforming catalyst being positioned at primary reform device upstream.The parallel feeding of steam and hydrocarbon is at high temperature fed to adiabatic pre-reformer.Pre-reforming product is heated again by combustion product gas, is fed to primary reform device subsequently.
By heating pre-reformer effluent stream, use pre-reformer that heat is back to process from flue gas recirculation, thus be reduced in the amount in reformer needed for combustion fuel.Owing to using less fuel, the stream carrying out the stack gas of reformer unit reduces, and causes less used heat.Use pre-reformer to have other benefit, such as, from the incoming flow of leading to primary reform device, remove higher hydrocarbon.
Because the size that can reduce primary reform device keeps high-level efficiency simultaneously, comprise the usual cost-effective of equipment of pre-reformer.
These methods reducing quantity of steam can be used for exporting steam and have little or nugatory situation.
When the benefit of the steam produced reasonably can not contribute to the efficiency of synthesis gas generation equipment, need method to alleviate the impact on facility efficiency.
When needs or when producing little output steam or do not need or produce output steam, need the impact alleviated facility efficiency.Be desirably in reforming process and produce hydrogen, produce simultaneously and seldom export steam or do not produce output steam, keep overall facility efficiency simultaneously.
Industrial expectation flexible design and operation have steam-hydrocarbon reforming process that steam that is limited or that reduce exports.
Industrial expectation has steam-hydrocarbon reforming process and the equipment of the energy efficiency of raising.
Industrial expectation reliable steam-hydrocarbon reforming process and equipment.
General introduction
The disclosure relates to steam-hydrocarbon reforming.
There is the aspect of some following general introductions.
An aspect #1. steam-hydrocarbon reforming method, described method comprises:
A reformate is introduced the first entrance of reactor by (), described reactor contains reforming catalyst, described reformate has the first temperature in of 550 DEG C of-725 DEG C of scopes or 600 DEG C of-700 DEG C of scopes, be enough under the reaction conditions forming other hydrogen in described reformate, under described reforming catalyst exists, described reformate is reacted, and under the first temperature out of 575 DEG C of-725 DEG C of scopes, first outlet of described reformate from described reactor is taken out;
B () is under the second temperature in of 800 DEG C of-975 DEG C of scopes, reformed gas is introduced the second entrance of described reactor, heat is transferred to the reformate described reactor from described reformed gas, and under the second temperature out of 675 DEG C of-925 DEG C of scopes or 700 DEG C-850 DEG C, second outlet of described reformed gas from described reactor is taken out;
C the reformer feed gas at least partially of the reformate of the first outlet comprised from described reactor is introduced in the multiple re-former tubes containing the second reforming catalyst by (), under the reaction conditions being enough to the described reformed gas formed containing hydrogen, under described second reforming catalyst exists, described reformate is reacted, and takes out described reformed gas from described multiple re-former tubes; With
D oxidant gas mixture containing aerobic and fuel is introduced the combustion parts of reformer by (), burn described fuel and oxygen to form combustion product gas and to produce heat, be used for described reformate with supplying energy to react in described multiple re-former tubes, and take out described combustion product gas from described combustion parts;
Wherein said reactor provides heat transfer surface area, described heat transfer surface area be used for described reformate in described reactor between the reaction period between described reformate and reformed gas indirect exchange heat, the temperature of described reformed gas is reduced to the second temperature out of 675 DEG C of-925 DEG C of scopes or 700 DEG C of-850 DEG C of scopes by wherein said heat transfer surface area effectively from the second temperature in of 800 DEG C of-975 DEG C of scopes, and keeps the first temperature out of described reformate to be 575 DEG C-725 DEG C.
The method of aspect #2. aspect #1, the wherein said reaction conditions being enough to be formed other hydrogen in described reformate comprises the temperature of 575 DEG C of-725 DEG C of scopes and the pressure of 500kPa-5000kPa scope, and the wherein said reaction conditions being enough to be formed described reformed gas comprises the temperature of 650 DEG C of-1000 DEG C of scopes and the pressure of 500kPa-5000kPa scope.
The method of aspect #3. aspect #1 or aspect #2, wherein said reformate has the hydrocarbon being less than 0.005 % by mole of C2 or more senior.
Any one method in aspect #4. aspect #1-#3, described method also comprises to be made described reformate and reformed gas in described reactor and flows (co-current) to pass through.
Any one method in aspect #5. aspect #1-#4, wherein said reformer feed gas comprises the reformate of the first outlet from described reactor based on mole flow velocity 90-100%.
Any one method in aspect #6. aspect #1-#4, wherein said reformer feed gas comprises all described reformate of the first outlet from described reactor.
Any one method in aspect #7. aspect #1-#5, wherein said reformer feed gas is the reformate of the first outlet from described reactor based at least 90% of mole flow velocity.
Any one method in aspect #8. aspect #1-#4, wherein said reformer feed gas is made up of all described reformate of the first outlet from described reactor.
Any one method in aspect #9. aspect #1-#8, wherein said reforming catalyst comprises the metal that at least one is selected from nickel, cobalt, platinum, palladium, rhodium, ruthenium and iridium.
Any one method in aspect #10. aspect #1-#9, described method also comprises:
By with described combustion product gas indirect heat exchange, heat packs is selected from the feed gas of the hydrocarbon of C1-C6 hydrocarbon containing steam and at least one;
Make the feed gas of described heating at least partially through tri-reforming catalyzer, with be enough under the reaction conditions reacted at least partially making the feed gas of described heating, under described tri-reforming catalyzer exists, make the reaction at least partially of the feed gas of described heating, thus form the first reformate; With
By with described combustion product gas indirect heat exchange, heat described first reformate at least partially, thus form the reformate of the first entrance introducing described reactor.
The method of aspect #11. aspect #10, is wherein enough to make the described reaction conditions reacted at least partially of the feed gas of described heating to comprise the temperature of 450 DEG C of-600 DEG C of scopes and the pressure of 500kPa-5000kPa scope.
The method of aspect #12. aspect #10 or aspect #11, wherein said reaction conditions is substantially adiabatic.
Any one method in aspect #13. aspect #10-#12, in wherein said feed gas, the molar ratio of steam and carbon is 1.8-2.8.
Any one method in aspect #14. aspect #1-#13, wherein after taking out described reformed gas from the second outlet of described reactor, not from described reformed gas removing sulphur compound.
Aspect #15. mono-kind is for implementing the equipment of the steam-hydrocarbon reforming method of any one in aspect #1-#14, and described equipment comprises:
Pre-reformer and interchanger, it is for the formation of described reformate;
There is the reformer of combustion parts, described combustion parts comprises burner, for described oxidant gas mixture and fuel are introduced in the combustion parts of described reformer, described reformer comprises the described multiple re-former tubes containing described second reforming catalyst, and each of described multiple re-former tubes has inlet end and exit end; With
Reactor, it has described first entrance be communicated with described pre-reformer downstream fluid flow, for accepting the reformate from described pre-reformer, described reactor contains described reforming catalyst, described reactor has described first exporting of being communicated with the inlet end upstream fluid flow of described multiple re-former tubes, described reactor has the second entrance be communicated with the exit end downstream fluid flow of described multiple re-former tubes, for accepting the reformed gas from described multiple re-former tubes, described reactor has the second outlet, for taking out described reformed gas under described second temperature out, and described reactor has heat transfer surface area, for indirect exchange heat between described reformate and reformed gas, the temperature of described reformed gas is reduced to the second temperature out of 675 DEG C of-925 DEG C of scopes or 700 DEG C of-850 DEG C of scopes by wherein said heat transfer surface area effectively from the second temperature in of 800 DEG C of-975 DEG C of scopes, and when described reformate being introduced the first entrance of described reactor under the first temperature in 575 DEG C of-725 DEG C of scopes or 600 DEG C of-700 DEG C of scopes, the first temperature out of described reformate is kept to be 575 DEG C-725 DEG C.
The equipment of aspect #16. aspect #15, wherein said equipment is for implementing in aspect #1-#14 the method for any one.
Several accompanying drawing summary
Fig. 1 comprises the process schematic that steam-hydrocarbon catalytic reforming unit, pre-reformer and air heat exchanges the steam-hydrocarbon reforming method and apparatus of reformer.
Fig. 2 is the process schematic of the steam-hydrocarbon reforming method and apparatus comprising steam-hydrocarbon catalytic reforming unit and pre-reformer.
Describe in detail
When being applied to any feature of the embodiment of the present invention described in specification sheets and claims, article used herein " " refers to one or more.Use " one " not restricted representation single features, restriction so unless specifically.Article before odd number or plural noun or noun phrase " is somebody's turn to do " and refers to specific specific features, and can have odd number or plural reference, and this depends on its context be used in.Adjective " any " refers to one, some or all of nondistinctive any amount.The term "and/or" of placing between first instance and second instance refer to following in one: (1) first instance, (2) second instance and (3) first instance and second instance.
Phrase " at least partially " refers to " part or all ".That flows can have the composition identical with the stream that it is derived from least partially.The specific components that can comprise the stream that it is derived from least partially of stream.
" fluid flow communication " used herein refers to by operability connections such as one or more conduit, manifold, valves, for transfering fluid.Conduit is any pipe, pipeline, path etc., can conveyance fluid by this conduit.Unless otherwise expressly specified, otherwise middle device can be there is between first device and the second device of fluid flow communication, such as pump, compressor or vessel.
" downstream " and " upstream " refers to the expected flow direction of the process fluid of transfer.If the expected flow direction of process fluid is from first device to the second device, then the second device is communicated with first device downstream fluid flow.
Term used herein " catalyzer " refers to catalytic material and any carrier for described catalytic material.
The disclosure relates to catalytic steam-hydrocarbon reforming.
Catalytic steam-hydrocarbon reforming, also referred to as catalytic steam reforming, steam methane reforming (SMR) or be called steam reformation simply, be defined through hydrocarbon and steam through catalyst reaction, being used for is any process of synthesis gas by reformer feedstock conversion.Use term " synthesis gas " (being commonly referred to synthetic gas) to represent any mixture comprising hydrogen and carbon monoxide herein.Reforming reaction is thermo-negative reaction, and usually can be described as
when producing synthesis gas, produce hydrogen.
Describing steam-hydrocarbon reforming process with reference to figure 1, showing the exemplary process flow diagram 1 for implementing described process.
This process comprises the first entrance reformate 40 being introduced the reactor 130 containing reforming catalyst 45.Reformate 40 is introduced the first entrance of reactor 130, it has the first temperature in of 550 DEG C of-725 DEG C of scopes or 600 DEG C of-700 DEG C of scopes.First temperature in is the temperature of the reformate 40 in first access point measurement.Be enough under the reaction conditions forming other hydrogen in reformate 50, under reforming catalyst 45 exists, reformate 40 reacted.The reaction conditions being enough to be formed other hydrogen in reformate can comprise the temperature of 575 DEG C of-725 DEG C of scopes and the pressure of 500kPa-5000kPa scope.Under the first temperature out of 575 DEG C of-725 DEG C of scopes, first outlet of reformate 50 from reactor 130 is taken out.First temperature out is the temperature at the first exit reformate 50.
Reformate is product containing reforming reaction and usually can contains any mixture of unreacted reactant (such as methane and steam).Reformate 40 can have the hydrocarbon of the C2 or more senior of lower concentration.Reformate 40 can have the hydrocarbon being less than 0.005 % by mole of C2 or more senior.In order to obtain the hydrocarbon of the C2 or more senior of lower concentration in reformate 40, the raw material containing C1-C6 hydrocarbon can be reformed with steam in pre-reformer.
Reformate 40 can be the effluent from pre-reformer." pre-reformer " is the reforming reactor before primary reform device." pre-reformer " for being synthesis gas by the feedstock conversion containing element hydrogen and elemental carbon, by with steam through catalyst reaction (with or without heats).Pre-reformer can be adiabatic fixed-bed reactor.Pre-reformer can be tubular reactor.Pre-reformer adopts the catalyzer dissimilar with primary reform device usually, such as high reactivity, high nickel content catalyzer.Temperature in pre-reformer can in about 450 DEG C of-Yue 600 DEG C of scopes.Towards pre-reformer heat can origin reformer unit or other source exhaust provide, but be usually characterised in that lack heated by combustion flame direct radiation.Pre-reformer and reformer can physical connections.
Pre-reformer is known in the art.The suitable material of structure and method are known.Use the advantage of pre-reformer to be that great majority or all heavy hydrocarbons (that is, C2+ hydrocarbon) in charging are converted into hydrogen and carbon oxides, thus be reduced in the possibility that in primary reform device, coke is formed.Another advantage using pre-reformer utilizes used heat to produce hydrogen and carbon oxides, thus the thermal load be reduced in primary reform device requires and reduces the amount of the excess steam of producing.
Pre-reformer can be different from primary reform device, because compared with pre-reformer, realizes the conversion being fed to the hydrocarbon larger proportion of process in primary reform device.
Fig. 1 shows a kind of exemplary, wherein in pre-reformer 120, forms reformate 40.By with combustion product gas 56 indirect heat exchange in the convection section 57 of primary reform device 100, heat packs is selected from the feed gas 10 of the hydrocarbon of C1-C6 hydrocarbon containing steam and at least one, thus forms the feed gas 20 of heating.
Steam and the carbon molar ratio of feed gas 10 can be 1.8-2.8.Steam and carbon molar ratio are that hydrogen is produced and the term of synthesis gas production field routine.Steam and carbon molar ratio (S/C ratio) are defined as in the hydrocarbon that enters in the charging of reformer, (always) ratio of the mole number of steam and the mole number of carbon atom.If mole flow velocity of such as steam is 6mol/s, mole flow velocity of methane is 1mol/s and mole flow velocity of ethane is 1mol/s, then steam and carbon molar ratio are 2.0.The methane of the 1mol/s carbon providing 1 mole per second, the ethane of the 1mol/s carbon providing 2 moles per second.The advantage of lower steam and carbon ratio is used to be improve the overall efficiency of steam-hydrocarbon reforming process.
Make the feed gas 20 of heating through reforming catalyst 25, and under the reaction conditions being enough to make the feed gas 20 of heating to react, reaction under reforming catalyst 25 exists, thus form reformate 30.The reaction conditions being enough to the feed gas 20 of heating is reacted can comprise the temperature of 450 DEG C of-600 DEG C of scopes and the pressure of 500kPa-5000kPa scope.Pre-reformer 120 can be adiabatic pre-reformer.Reaction conditions for the formation of reformate 30 can be thermal insulation substantially.By in the convection section 57 of reformer 100 with combustion product gas 54 indirect heat exchange, heated reformate product 30, to form the reformate 40 of the first entrance introducing reactor 130.
Reactor 130 is containing reforming catalyst 45.Reforming catalyst 45 can be any suitable reforming catalyst known in the art.The catalytic material of reforming catalyst 45 can be the metal that one or more are selected from nickel, cobalt, platinum, palladium, rhodium, ruthenium and iridium.Reforming catalyst 45 can be the catalyzer of load, and wherein carrier comprises one or more in the aluminum oxide of high-temperature stable, calcium aluminate and magnesium aluminate.Reforming catalyst is well-known and commercially available, and easily can select suitable catalyzer and without the need to undo experimentation.
Reforming catalyst 45 also can be structurizing catalyst filling.Catalystic material is applied to structurizing catalyst filling by washcoat (washcoat) technique.
As shown in Figure 1, reformed gas 70 is introduced the second entrance of reactor 130.According to this process, under the second temperature in of 820 DEG C of-970 DEG C of scopes, introduce reformed gas 70.Second temperature in is the temperature of the second ingress reformed gas 70 at reactor 130.By indirect heat transfer in reactor 130, heat is passed to reformate 40 from reformed gas 70.Reformate 40 and reformed gas 70 can flow through in reactor 130.Concurrent flow, also referred to as common flowing or split flow, flows through device for wherein flowing with the identical direction of cardinal principle.Concurrent flow can be contrary with counter-current flow, in counter-current flow, flow with each other substantially relative direction flow through device.Concurrent flow can be contrary with cross-flow, and in cross-flow, a plume is generally perpendicular to the flowing of another plume.
Under the second temperature out of 675 DEG C of-925 DEG C of scopes or 700 DEG C of-850 DEG C of scopes, take out reformed gas 80 from the second outlet of reactor 130.Second temperature out is the temperature of the second exit reformed gas 80 at reactor 130.
This process comprises introduces multiple re-former tubes 65 containing the second reforming catalyst 67 by reformer feed gas 60.Primary reform device 100 comprises the multiple re-former tubes 65 in the combustion parts 53 of primary reform device 100.Reformer feed gas 60 comprises to come the reformate 50 of the first outlet of autoreactor 130 at least partially.Reformer feed gas 60 can comprise to come autoreactor 130 first outlet reformate 50 based on mole 90-100%, the reformate 50 of its small portion is for another object (not shown).Reformer feed gas 60 can comprise to come all reformates 50 of the outlet of autoreactor 130.Reformer feed gas 60 can be the reformate 50 of the first outlet of autoreactor 130 based at least 90% of mole flow velocity, another part provides (not shown) by another source.Reformer feed gas 60 can all reformates composition of the first outlet of origin autoreactor 130.
Under the reaction conditions being enough to the reformed gas 70 formed containing hydrogen, under reforming catalyst 67 exists, the feed gas 60 comprising reformate 50 is reacted.The reaction conditions being enough to be formed reformed gas 70 comprises the temperature of 650 DEG C of-1000 DEG C of scopes and the pressure of 500kPa-5000kPa scope.Reformed gas 70 is taken out from multiple re-former tubes 65.
Re-former tubes is known in the art.Being fabricated to of re-former tubes is known in the art.
Reforming catalyst 67 can be any suitable reforming catalyst known in the art.Reforming catalyst 67 can be identical or different with reforming catalyst 45.Reforming catalyst is well-known and commercially available, and easily can select suitable catalyzer and without the need to undo experimentation.
This process comprises to be introduced in the combustion parts 53 of reformer 100 by fuel 52 with containing the oxidant gas mixture 51 of aerobic.Oxidant gas mixture 51 and fuel 52 is introduced by burner 55.Reformer 100 can be lower roasting kiln, side roasting kiln (not shown), upper roasting kiln (not shown) as shown in Figure 1, or any suitable combination.Oxidant gas mixture 51 and fuel 52 can be introduced and/or premix separately through burner 55.Fuel and/or oxygenant can be sprayed into (namely stage by stage) combustion parts.Fuel can be any suitable fuel known in the art.Such as fuel can comprise from least one in the byproduct gas of the refuse fuel etc. of pressure swing adsorption device, Sweet natural gas, refinery fuel gas body, neighbouring process.Oxidant gas mixture 51 can be any suitable oxidant gas, such as air, industrial oxygen, oxygen-rich air or oxygen-denuded air.By in the convection section of reformer 100 with combustion product gas indirect heat exchange, can heated oxidant gaseous mixture.Fuel and oxygen burn in combustion parts 53, to form combustion product gas 54, thus produce heat for the energy being applied to the feed gas that comprises reformate and reacting in multiple re-former tubes 65.Combustion product gas 54 is taken out from combustion parts 53.
The structure of the reformer containing the re-former tubes for the production of hydrogen and/or synthesis gas and be operating as well-known.
Reactor 130 provides heat transfer surface area.At reformate in reactor 130 between the reaction period, heat transfer surface area is indirect exchange heat between reformate 40 and reformed gas 70.The temperature of reformed gas 70 is reduced to the second temperature out of 675 DEG C of-925 DEG C of scopes or 700 DEG C of-850 DEG C of scopes by the amount of heat transfer surface area effectively from the second temperature in of 800 DEG C of-975 DEG C of scopes, and keeps the first temperature out of reformate 50 to be 575 DEG C-725 DEG C.
Although routine is the maximum heat transfer of the reformed gas making always reformer unit, to improve process efficiency and to avoid producing other output steam, but contriver finds, heat transfer surface area in limited reactions device described above thus keep the temperature in reactor, there is provided and avoid advantage Metal Dusting in the reactor, obtain the major part of efficiency benefits simultaneously.
The technician with knowledge of the present disclosure easily can realize the design of the reactor with suitable heat transfer surface area, Material selec-tion, structure and operation.
Due to by avoiding Metal Dusting according to this process operation, do not need as prior art, introduce sulphur compound Metal Dusting to avoid.Therefore, can this process be carried out, and do not remove sulphur compound from reformed gas 80 after taking out reformed gas 80 from the second outlet of reactor 130.This provide the advantage of the equipment avoided needed for removal of sulphur.
With reference to figure 1, the equipment for carrying out steam-hydrocarbon reforming process comprises pre-reformer 120 for the formation of reformate 40 and interchanger 15 and 25.This equipment also comprises the reformer 100 with combustion parts 53, and this combustion parts 53 comprises burner 55, for oxidant gas mixture 51 and fuel 52 being introduced in combustion parts 53.Reformer 100 comprises the multiple re-former tubes 65 containing reforming catalyst 67, and each of described multiple re-former tubes 65 has inlet end and exit end.
This equipment also comprises reactor 130, and it has the first entrance be communicated with pre-reformer 120 downstream fluid flow via interchanger 25, for accepting the reformate 40 from pre-reformer 120.Reactor 130 is containing reforming catalyst 45.First outlet of reactor 130 is communicated with the inlet end upstream fluid flow of multiple re-former tubes 65.Second entrance of reactor 130 is communicated with the exit end downstream fluid flow of multiple re-former tubes 65, for accepting the reformed gas 70 from multiple re-former tubes 65.Reactor 130 has the second outlet, for taking out reformed gas 80 under the second temperature out.Reactor 130 has heat transfer surface area, for indirect exchange heat between reformate and reformed gas, the temperature of reformed gas is effectively reduced to the second temperature out of 675 DEG C of-925 DEG C of scopes or 700 DEG C of-850 DEG C of scopes by wherein said heat transfer surface area from the second temperature in of 800 DEG C of-975 DEG C of scopes, and when reformate being introduced under the first temperature in 550 DEG C of-725 DEG C of scopes or 600 DEG C of-700 DEG C of scopes the first entrance of reactor 130, the first temperature out keeping reformate is 575 DEG C-725 DEG C.
As shown in Figure 1, reformed gas 80 can be optionally treated to reclaim heat and/or to provide the hydrogen product 172 of purifying.Reformed gas 80 can be led to boiler 140, to produce steam by indirect heat transfer.The reformed gas 80 of cooling can be led to water-gas shift reactor 150, so that CO is converted into CO
2, produce more hydrogen simultaneously.One or more conversion reactor can be used.Conversion reactor is well-known.Conversion can be the conversion of high temperature, middle temperature or low temperature.Reformed gas 80 can cool further in interchanger 160, leads to pressure swing adsorption device 170 subsequently.Reformed gas 80 is separated, to produce hydrogen product stream 172 and byproduct stream 174 in pressure swing adsorption device 170.Byproduct stream 174 can be used as fuel 52 in reformer 100.
The product of production is depended in the configuration of downstream processing, such as hydrogen or synthesis gas.The details of downstream processing also depends on the preference of the producer.
Embodiment
Use business process simulation software Aspen
, simulate some embodiments.
In each example, Sweet natural gas is for being fed to pre-reformer and as the postcombustion for burning in reformer.Postcombustion for burning in reformer is sometimes referred to as " modification fuel ".Major part for the fuel burnt in reformer is the byproduct gas 174,374 from pressure swing adsorption device 170.Use the Sweet natural gas of same composition in each example.
Result comprises the ratio S/S of steam S for reforming and the total steam produced during the course
t, and normalized clean than and normalizedly slightly comparing energy.The total steam S produced
tfor pressure is greater than total steam of the production of 2Mpa.At S
tin do not comprise the low-grade steam that pressure is less than 2MPa.Any relative steam excessive for the amount of reforming produced may be output to another process, and is called " output steam ".
Can based on thick than energy and/or only than the overall efficiency of energy evaluation procedure.Taking it by and large, thick than can for preparing the energy needed for a certain amount of hydrogen, and clean than can for preparing the energy needed for a certain amount of hydrogen, and the steam of generation counts as energy by it.Below provide definition.
Thick be following sum than energy GSE: the higher thermal value (J/Nm introducing the postcombustion of combustion parts
3) HHV
fuelbe multiplied by the flow velocity (Nm of fuel
3/ h) F
fuel, and the higher thermal value (J/Nm of the reformer raw material of introducing reformer
3) HHV
feedbe multiplied by the flow velocity (Nm of reformer raw material
3/ h) F
feed, by this summation divided by hydrogen throughput rate (Nm
3/ h) HPR, with unit J/Nm
3represent; Be mathematically
Clean ratio energy NSE is the higher thermal value (J/Nm of the postcombustion introducing combustion parts
3) HHV
fuelbe multiplied by fuel flow rate (Nm
3/ h) F
fuel, add the higher thermal value (J/Nm of the reformer raw material introducing reformer
3) HHV
feedbe multiplied by the flow velocity (Nm of reformer raw material
3/ h) F
feed, deduct the enthalpy difference Δ H (in J/kg) exported between steam and water at 25 DEG C and be multiplied by the mass rate F exporting steam
steam(in kg/h), all divided by hydrogen throughput rate (Nm
3/ h) HPR, with unit J/Nm
3represent; Be mathematically
Owing to being not counted in output steam, thick than can always be more than or equal to only than energy.When not having steam to export, thick than can and only equal than energy.
By the clean ratio energy normalization method of all ratio energy results in table 1 relative to embodiment 1, the clean ratio of embodiment 1 can give the base value of 100.
Embodiment 1-comparative example
Fig. 2 illustrates process flow Fig. 2 of prior art arrangement.
The pre-reformer feed gas 10 that will be made up of steam and Sweet natural gas (wherein steam and carbon molar ratio are 2.5) heats in interchanger 15, and the pre-reformer feed gas 20 of heating reacts through pre-reformer catalyzer 25 in pre-reformer 120.Take out reformate 30 from pre-reformer 120, and heat in interchanger 25, to form the reformate of heating, it can be used as reformer feed gas 260 to lead to multiple re-former tubes 65.Reformer feed gas 260 reacts through reforming catalyst 67, and takes out as reformed gas 270 from multiple re-former tubes 65.Reformed gas 270 is led to boiler 140 to produce steam, thus cooling reformed gas 270.The reformed gas 270 of cooling is led to conversion reactor 150, so that CO is converted into CO
2, and in reformed gas, form other H
2.Reformed gas through conversion is led to air-cooler 160, prepares with condensation of water with for reformation gaseous tension swing adsorption device 170.Reformed gas is separated in pressure swing adsorption device 170, to form hydrogen product 372 and pressure swing adsorption device by product 374.
Via burner 55, fuel 252 and air 251 are introduced reformer 100, and burns, to be provided for the heat of the reforming reaction in multiple reformer tubes 65.Fuel 252 comprises pressure swing adsorption device by product 374 and postcombustion.Postcombustion is Sweet natural gas.By in the convection section 158 of reformer 100 with single stage and combustion product gas heat exchange by preheating of air.By in interchanger 15 with combustion product gas 256 indirect heat exchange, heating pre-reformer feed gas 10.By in interchanger 25 with combustion product gas 254 indirect heat exchange, heated reformate product 30.After combustion product gas has the pre-reformer feed gas 10 of heating, reformate 30 and combustion air 251, combustion product gas is led to boiler 180, to produce steam.
Via from the reformed gas in boiler 140 and from the combustion product gas heat recuperation boiler 180, production of steam is maximized, and the process according to embodiment 1 is optimized, and counts to provide export steam minimum clean than can NSE.Be optimized under the combustion air preheating temperature provided by single stage air preheating.The results are summarized in table 1.
For the ratio S/S of the steam reformed and the total steam produced during the course
tbe 0.45.This means that this process produces the amount more than 2 times that reform required in process.
The process flow 260 entering the re-former tubes 65 containing catalyzer has molar fraction ratio R, wherein
wherein Y
cH4for the molar fraction of methane in process flow, Y
h2for the molar fraction of hydrogen in process flow, and Y
cO2for the molar fraction of carbonic acid gas in process flow.Contriver finds, provides carbon in the instruction containing the trend that the reforming catalyst in the pipe of catalyzer is formed at the molar fraction ratio introducing the stream contained in the pipe of catalyzer in burning reformer.
The molar fraction ratio R of lower value is corresponding to the comparatively low propensity that the catalyzer of carbon in re-former tubes is formed.
Molar fraction ratio R=2.86 of embodiment 1.
Be 100 by being normalized to NSE according to the process of embodiment 1.The GSE of embodiment 1 is 119.
The comparative example that the steam that embodiment 2-has reduction exports
Process flow diagram flow chart in Fig. 2 is also applicable to embodiment 2.By improving air preheating temperature, reduce the amount of the steam formed.By point two stages by preheating of air, improve air preheating temperature.Embodiment 1 has the single preheating of air stage, and embodiment 2 has two preheating of air stages.In addition, embodiment 2 is identical with embodiment 1.To the air preheating temperature optimizing process that two benches preheating of air provides, minimum clean than energy to realize, keep molar fraction ratio R identical with embodiment 1 simultaneously.
The steam of embodiment 2 is substantially the same with carbon molar ratio S/C and embodiment 1.
The amount of excess steam produced in embodiment 2 is significantly less than embodiment 1, as by the ratio S/S of the steam for reforming with the total steam produced during the course
tproved.The S/S of embodiment 2
tbe 0.64, comparing embodiment 1 is 0.45.
Although clean than being increased to 101.3 of embodiment 2 from 100 of embodiment 1, but it is thick than being reduced to 110.2 of embodiment 2 from 118.9 of embodiment 1, show and change prior art process, to reduce the impact of the output steam of unwanted or lesser value by improving air preheating temperature.
The steam of embodiment 3-gas heat exchange reformer and reduction exports
Fig. 1 illustrates process flow Fig. 1 of embodiment 3.Identical with embodiment 2, embodiment 3 also uses two preheating of air stages.
Embodiment 3 comprises gas heat exchange reformer 130, and by this process optimization, to provide minimum clean than energy NSE for the reformate temperature in of specifying 649 DEG C and the reformed gas outlet temperature 788 DEG C of specifying, maintenance molar fraction ratio R is less than those of embodiment 1 and 2 simultaneously.The molar fraction ratio R of embodiment 3 does not keep the value identical with 2 with embodiment 1, because postcombustion value vanishing in optimization, this is that those skilled in the art understand situation about avoiding.Molar fraction ratio R is subject to the impact of steam and carbon molar ratio, and described ratio can be reduced to the molar fraction ratio R that 2.3 provide about 1.12 simultaneously.The present invention protected as requested, limits into and goes out the temperature that air heat exchanges reformer 130.
The pre-reformer feed gas 10 that will be made up of steam and methane (wherein steam and carbon molar ratio are 2.3) heats in interchanger 15, and the pre-reformer feed gas 20 of heating reacts through pre-reformer catalyzer 25 in pre-reformer 120.For this embodiment, pre-reformer 120 is adiabatic.Compare with 2 with embodiment 1, according to this process, use pre-reformer 120 and reactor 130 to allow to use lower steam and carbon molar ratio, and the carbon do not improved forms risk (the molar fraction ratio R illustration by lower).Take out reformate 30 from pre-reformer 120, and by the convection section 57 of reformer 100 with combustion product gas 54 indirect heat exchange, in interchanger 25 heat, to form the reformate 40 of heating.
The reformate 40 of heating is led to reactor 130, and reacts through reforming plant catalyst 45 in reactor 130, to form other hydrogen in reformate 50.Reformate 50 is led to multiple re-former tubes 65 as reformer feed gas 60.Reformer feed gas 60 reacts through reforming catalyst 67, and takes out as reformed gas 70 from multiple re-former tubes 65.Reformed gas 70 is led to boiler 130, to be provided for the heat of the reaction of reformate 40, and takes out as reformed gas 80 from reactor 130.By indirect heat transfer in reactor 130, heat is transferred to reformate 40 from reformed gas 70.By reformate 40 and reformed gas 70 in reactor 130 each other and flow through.Reformed gas 80 is led to boiler 140 to produce steam, thus cooling reformed gas 80.The reformed gas 80 of cooling is led to conversion reactor 150, so that CO is converted into CO
2, and in reformed gas, form other H
2.Reformed gas through conversion is led to air-cooler 160, prepares with condensation of water with for reformation gaseous tension swing adsorption device 170.Reformed gas is separated in pressure swing adsorption device 170, to form hydrogen product 172 and pressure swing adsorption device by product 174.
Via burner 55, fuel 52 and air 51 are introduced in reformer 100, and burns, to be provided for the heat of the reforming reaction in multiple reformer tubes 65.By in the convection section 57 of reformer 100 with combustion product gas heat exchange, by preheating of air.By in interchanger 15 with combustion product gas 56 indirect heat exchange, heating pre-reformer feed gas 10.By in interchanger 25 with combustion product gas 54 indirect heat exchange, heated reformate product 30.After combustion product gas has the pre-reformer feed gas 10 of heating, reformate 30 and combustion air 51, combustion product gas is led to boiler 180, to produce steam.
Compared with embodiment 1, provide higher air preheating temperature according to the process of embodiment 3, to reduce the amount exporting steam.The air preheating temperature of embodiment 3 is less than embodiment 2, but compared with embodiment 2, still produces less output steam in embodiment 3.Steam is produced via from the reformed gas in boiler 140 and from the combustion product gas heat recuperation boiler 180.Table 1 is the results are summarized in from this model.
The amount of the excess steam produced in embodiment 3 is significantly less than embodiment 1, as by for the steam the reformed ratio S/S with the total steam produced during the course
tproved.The S/S of embodiment 3
tbe 0.65, comparing embodiment 1 is 0.45.The amount of excess steam produced in embodiment 3 is suitable with the amount of the excess steam of embodiment 2.
But the clean ratio of embodiment 3 can be less than the clean of embodiment 1 and 2 and compare energy.In addition, the thick of any one that the thick ratio of embodiment 3 can be less than in embodiment 1 and 2 compares energy.Embodiment 3 illustrates the efficiency using the reformer (reactor 130) of gas heating how to improve process, especially when exporting steam demand and being low.
As mentioned above, the temperature that enters and exit of the reformer (reactor 130) of gas heating is confined to scope claimed in embodiment 3, and is summarized in table 2.The temperature of stream 40 is appointed as T40, and the temperature of stream 50 is appointed as T50 etc.
The steam of embodiment 4-gas heat exchange reformer and reduction exports
Fig. 1 illustrates process flow Fig. 1 of embodiment 4.Embodiment 4 also comprises two preheating of air stages.
Embodiment 4 is similar to Example 3, and difference is, the reformer (reactor 130) of gas heating enter and exit temperature outside claimed scope.By this process optimization, to provide minimum clean than energy NSE for the reformate temperature in of specifying 538 DEG C and the reformed gas outlet temperature 593 DEG C of specifying, maintenance molar fraction ratio R is less than those of embodiment 1 and 2 simultaneously.Compared with embodiment 3, the process of embodiment 4 improves the thermal load of the reformer (reactor 130) of gas heating.The reformate temperature in of specifying and the reformed gas outlet thermal creep stress of specifying are outside claimed scope.The molar fraction ratio R of embodiment 4 does not keep the value identical with 2 with embodiment 1, because postcombustion value vanishing in optimization, this is that those skilled in the art understand situation about avoiding.Molar fraction ratio R is subject to the impact of steam and carbon molar ratio, and described ratio can be reduced to 2.3, provides the molar fraction ratio R of about 0.85 simultaneously.The temperature that enters and exit of gas heat exchange reformer 130 is not limited to the present invention protected as requested, and outside the scope required by claimed process.
Compared with embodiment 1, provide higher air preheating temperature according to the process of embodiment 4, to reduce the amount exporting steam.The air preheating temperature of embodiment 4 is less than embodiment 2 and is less than embodiment 3, but compared with embodiment 2 or 3, still produces less output steam in embodiment 4.Steam is produced via from the reformed gas in boiler 140 and from the combustion product gas heat recuperation boiler 180.Table 1 is the results are summarized in from this model.
The amount of excess steam of producing in embodiment 4 is significantly less than embodiment 1, as by the ratio S/S of the steam for reforming with the total steam produced during the course
tproved.The S/S of embodiment 4
tbe 0.68, comparing embodiment 1 is 0.45.
As mentioned above, the reformer (reactor 130) of gas heating to enter and exit temperature unrestricted in example 4, and be summarized in table 2.That flows 40 temperature is appointed as T40, and the temperature of stream 50 is appointed as T50 etc.
The clean of any one that the clean ratio of embodiment 4 can be less than in embodiment 1,2 and 3 compares energy.In addition, the thick of any one that the thick ratio of embodiment 4 can be less than in embodiment 1,2 and 3 compares energy.Embodiment 4 illustrates the efficiency using the reformer (reactor 130) of gas heating how to improve process, especially when not needing to export steam.
Although the efficiency of embodiment 4 is better than the efficiency that embodiment 3 calculates, contriver finds, and such operation can cause high risk Metal Dusting in reactor 130.Therefore, provide enough efficiency to improve according to the operation of the process of embodiment 3, keep the reliability of equipment simultaneously.
Although describe the present invention with regard to specific embodiment or embodiment, the present invention is not limited to this, but can not depart from scope of the present invention defined in the appended claims and change or be revised as any other different forms.
Table 1.
Table 2.
Claims (14)
1. steam-hydrocarbon reforming method, described method comprises:
A reformate is introduced the first entrance of reactor by (), described reactor contains reforming catalyst, described reformate has the first temperature in of 550 DEG C of-725 DEG C of scopes, be enough under the reaction conditions forming other hydrogen in described reformate, under described reforming catalyst exists, described reformate is reacted, and under the first temperature out of 575 DEG C of-725 DEG C of scopes, first outlet of described reformate from described reactor is taken out;
B () is under the second temperature in of 800 DEG C of-975 DEG C of scopes, reformed gas is introduced the second entrance of described reactor, make described reformate and reformed gas in described reactor and flow through, heat is transferred to the reformate described reactor from described reformed gas, and under the second temperature out of 675 DEG C of-925 DEG C of scopes, second outlet of described reformed gas from described reactor is taken out;
C the reformer feed gas at least partially of the reformate of the first outlet comprised from described reactor is introduced in the multiple re-former tubes containing the second reforming catalyst by (), under the reaction conditions being enough to the described reformed gas formed containing hydrogen, under described second reforming catalyst exists, described reformate is reacted, and takes out described reformed gas from described multiple re-former tubes; With
D oxidant gas mixture containing aerobic and fuel is introduced the combustion parts of reformer by (), burn described fuel and oxygen to form combustion product gas and to produce heat, be used for described reformate with supplying energy to react in described multiple re-former tubes, and take out described combustion product gas from described combustion parts;
Wherein said reactor provides heat transfer surface area, described heat transfer surface area be used for described reformate in described reactor between the reaction period between described reformate and reformed gas indirect exchange heat, the temperature of described reformed gas is reduced to the second temperature out of 675 DEG C of-925 DEG C of scopes by wherein said heat transfer surface area effectively from the second temperature in of 800 DEG C of-975 DEG C of scopes, and keeps the first temperature out of described reformate to be 575 DEG C-725 DEG C; And
Wherein after taking out described reformed gas from the second outlet of described reactor, not from described reformed gas removing sulphur compound.
2. the process of claim 1 wherein that described first temperature in is 600 DEG C of-700 DEG C of scopes, and described second temperature out is 700 DEG C of-850 DEG C of scopes.
3. the method for claim 1, the wherein said reaction conditions being enough to be formed other hydrogen in described reformate comprises the temperature of 575 DEG C of-725 DEG C of scopes and the pressure of 500 kPa-5000 kPa scopes, and the wherein said reaction conditions being enough to be formed described reformed gas comprises the temperature of 650 DEG C of-1000 DEG C of scopes and the pressure of 500 kPa-5000 kPa scopes.
4. the process of claim 1 wherein that described reformate has the hydrocarbon being less than 0.005 % by mole of C2 or more senior.
5. the process of claim 1 wherein that described reformer feed gas comprises reformate from the first outlet of described reactor based on the 90-100% of mole flow velocity.
6. the process of claim 1 wherein that described reformer feed gas comprises all described reformate of the first outlet from described reactor.
7. the process of claim 1 wherein that described reformer feed gas is the reformate of the first outlet from described reactor based at least 90% of mole flow velocity.
8. the process of claim 1 wherein that described reformer feed gas is made up of all described reformate of the first outlet from described reactor.
9. the method for claim 1, described method also comprises:
By with described combustion product gas indirect heat exchange, heat packs is selected from the feed gas of the hydrocarbon of C1-C6 hydrocarbon containing steam and at least one;
Make the feed gas of described heating at least partially through tri-reforming catalyzer, with be enough under the reaction conditions reacted at least partially making the feed gas of described heating, under described tri-reforming catalyzer exists, make the reaction at least partially of the feed gas of described heating, thus form the first reformate; With
By with described combustion product gas indirect heat exchange, heat described first reformate at least partially, thus form the reformate of the first entrance introducing described reactor.
10. the method for claim 9, is wherein enough to make the described reaction conditions reacted at least partially of the feed gas of described heating to comprise the temperature of 450 DEG C of-600 DEG C of scopes and the pressure of 500 kPa-5000 kPa scopes.
The method of 11. claims 9, the described reaction conditions wherein for the formation of described first reformate is substantially adiabatic.
The method of 12. claims 9, in wherein said feed gas, the molar ratio of steam and carbon is 1.8-2.8.
13. 1 kinds of equipment of steam-hydrocarbon reforming method for implementing the claims 1, described equipment comprises:
Pre-reformer and interchanger, it is for the formation of described reformate;
There is the reformer of combustion parts, described combustion parts comprises burner, for described oxidant gas mixture and fuel are introduced in the combustion parts of described reformer, described reformer comprises the described multiple re-former tubes containing described second reforming catalyst, and each of described multiple re-former tubes has inlet end and exit end; With
Reactor, it has described first entrance be communicated with described pre-reformer downstream fluid flow, for accepting the reformate from described pre-reformer, described reactor contains described reforming catalyst, described reactor has described first exporting of being communicated with the inlet end upstream fluid flow of described multiple re-former tubes, described reactor has the second entrance be communicated with the exit end downstream fluid flow of described multiple re-former tubes, for accepting the reformed gas from described multiple re-former tubes, described reactor has the second outlet, for taking out described reformed gas under described second temperature out, and described reactor has heat transfer surface area, for indirect exchange heat between described reformate and reformed gas, the temperature of described reformed gas is reduced to the second temperature out of 675 DEG C of-925 DEG C of scopes by wherein said heat transfer surface area effectively from the second temperature in of 800 DEG C of-975 DEG C of scopes, and when described reformate being introduced the first entrance of described reactor under the first temperature in 550 DEG C of-725 DEG C of scopes, the first temperature out of described reformate is kept to be 575 DEG C-725 DEG C.
The equipment of 14. claims 13, the temperature of described reformed gas is reduced to the second temperature out of 700 DEG C of-850 DEG C of scopes by wherein said heat transfer surface area effectively from the second temperature in of 800 DEG C of-975 DEG C of scopes, and when described reformate being introduced the first entrance of described reactor under the first temperature in 600 DEG C of-700 DEG C of scopes, keep the first temperature out of described reformate to be 575 DEG C-725 DEG C.
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| US12/914,489 US8287763B2 (en) | 2010-10-28 | 2010-10-28 | Steam-hydrocarbon reforming with limited steam export |
| US12/914,489 | 2010-10-28 | ||
| PCT/US2011/050776 WO2012057922A1 (en) | 2010-10-28 | 2011-09-08 | Steam-hydrocarbon reforming with limited steam export |
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- 2011-09-08 WO PCT/US2011/050776 patent/WO2012057922A1/en active Application Filing
- 2011-09-08 ES ES11761194.7T patent/ES2681604T3/en active Active
- 2011-09-08 CN CN201180063480.0A patent/CN103298735B/en active Active
- 2011-09-08 EP EP11761194.7A patent/EP2632852B1/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| US20120104321A1 (en) | 2012-05-03 |
| CN103298735A (en) | 2013-09-11 |
| EP2632852A1 (en) | 2013-09-04 |
| WO2012057922A1 (en) | 2012-05-03 |
| CA2814753C (en) | 2015-12-29 |
| US8449633B2 (en) | 2013-05-28 |
| ES2681604T3 (en) | 2018-09-14 |
| US20120282145A1 (en) | 2012-11-08 |
| EP2632852B1 (en) | 2018-05-16 |
| CA2814753A1 (en) | 2012-05-03 |
| US8287763B2 (en) | 2012-10-16 |
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